KR20250017536A - Rechargeable lithium battery including the same - Google Patents

Abstract

A lithium secondary battery is provided, comprising: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and an electrolyte, wherein the negative electrode has a composite density of 1.7 g/cc or more, and the electrolyte comprises: a lithium salt; a non-aqueous organic solvent; a first additive represented by the following chemical formula 1; a second additive represented by the following chemical formula 2; and a third additive represented by the following chemical formula 3. [Chemical formula 1] [Chemical formula 2] [Chemical formula 3]. (The description of each of the chemical formulas above follows the specification.)

Description

LITHIUM SECONDARY BATTERY{RECHARGEABLE LITHIUM BATTERY INCLUDING THE SAME}

It's about lithium secondary batteries.

Recently, with the rapid spread of electronic devices that use batteries, such as mobile phones, laptop computers, and electric vehicles, the demand for high energy density and high capacity secondary batteries is rapidly increasing. Accordingly, research and development to improve the performance of lithium secondary batteries is actively being conducted.

A lithium secondary battery is a battery that includes a cathode and an anode that contain active materials capable of intercalating and deintercalating lithium ions, and an electrolyte, and produces electrical energy through oxidation and reduction reactions when lithium ions are intercalated/deintercalated from the cathode and anode.

One of the recent development directions for lithium secondary batteries is to increase the density of the negative electrode. However, increasing the density of the negative electrode reduces the void volume, which increases the amount of electrolyte impregnated in the negative electrode, and causes an increase in the thickness of the battery and a decrease in its lifespan.

One embodiment provides a lithium secondary battery that suppresses an increase in battery thickness and a decrease in lifespan while increasing the density of the negative electrode.

One embodiment provides a lithium secondary battery, comprising: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and an electrolyte, wherein the composite density of the negative electrode is 1.7 g/cc or more, and the electrolyte comprises: a lithium salt; a non-aqueous organic solvent; a first additive represented by the following chemical formula 1; a second additive represented by the following chemical formula 2; and a third additive represented by the following chemical formula 3:

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

.

.

A lithium secondary battery according to one embodiment can suppress an increase in battery thickness and a decrease in lifespan while increasing the density of the negative electrode.

Figures 1 to 4 are schematic diagrams illustrating a lithium secondary battery according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims described below.

Unless otherwise specified herein, when a part such as a layer, film, region, or plate is said to be “over” another part, this includes not only cases where it is “directly over” the other part, but also cases where there are other parts in between.

Unless otherwise specified herein, the singular may also include the plural. In addition, unless otherwise specified, "A or B" may mean "including A, including B, or including A and B."

As used herein, the term "combination thereof" may mean mixtures, laminates, composites, copolymers, alloys, blends, reaction products, and the like of the components.

In this specification, the “composite density of the negative electrode” is a value calculated by dividing the weight of the components (active material, conductive material, binder, etc.) excluding the current collector in the negative electrode by the volume.

Unless otherwise defined in the chemical formulas herein, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

As used herein, “fluoroalkyl group” means an alkyl group in which some or all of the hydrogen atoms are replaced with fluorine atoms.

As used herein, “perfluoroalkyl group” means an alkyl group in which all of the hydrogen atoms are replaced with fluorine atoms.

(lithium secondary battery)

One embodiment provides a lithium secondary battery, comprising: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and an electrolyte, wherein the composite density of the negative electrode is 1.7 g/cc or more, and the electrolyte comprises: a lithium salt; a non-aqueous organic solvent; a first additive represented by the following chemical formula 1; a second additive represented by the following chemical formula 2; and a third additive represented by the following chemical formula 3:

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

.

.

The above first and third additives function as surfactants having both a hydrophilic group and a hydrophobic group within one molecule.

Specifically, the first additive comprises an ether group at the center and a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms on both sides thereof. Here, the ether group is a hydrophilic group, and the fluorine atom or the fluoroalkyl group having 1 to 10 carbon atoms is a hydrophobic group.

In addition, the third additive comprises a ketone group at the center and a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms on both sides thereof. Here, the ketone group is a hydrophilic group, and the fluorine atom or the fluoroalkyl group having 1 to 10 carbon atoms is a hydrophobic group.

Accordingly, when an electrolyte solution containing the first additive and the third additive is used at the same time, wettability for the positive and negative electrodes is improved, so that lithium cations (Li ⁺ ) are uniformly formed at the interface between the positive electrode and the electrolyte, and a stable SEI film is formed at the interface between the negative electrode and the electrolyte, thereby suppressing precipitation of lithium dendrites.

Meanwhile, the second additive is a fluoro-substituted oxalate borate compound, wherein the fluoro group stabilizes a lithium salt (e.g., LiPF ₆ ).

Accordingly, when an electrolyte solution containing the second additive is used, the generation of HF is suppressed, thereby preventing the elution of transition metals from the positive electrode active material and damage to the SEI film at the interface between the negative electrode and the electrolyte.

Therefore, by using an electrolyte containing the first to third additives simultaneously, the composite density of the negative electrode can be increased to 1.7 g/cc or more, while suppressing an increase in the thickness of the battery and a decrease in the lifespan.

Hereinafter, a lithium secondary battery according to an embodiment is described in more detail.

Negative composite density

Generally known lithium secondary batteries use a negative electrode having a composite density of less than 1.7 g/cc, but a lithium secondary battery according to one embodiment uses a negative electrode having a composite density of 1.7 g/cc or more.

The upper limit for the composite density of the above negative electrode is not particularly limited, but may be 2.0 g/cc or less, 1.9 g/cc or less, or 1.8 g/cc or less.

Additive 1

In the above chemical formula 1, R ¹ and R ² are each independently a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

For example, R ¹ can be a fluoroalkyl group having 2 carbon atoms.

Additionally, R ² can be a fluoroalkyl group having 3 carbon atoms.

The above first additive can be represented by the following chemical formula 1-1:

[Chemical Formula 1-1]

In the chemical formula 1-1, R ¹¹ to R ¹⁵ are each a hydrogen atom or a fluorine atom, and at least one of R ¹¹ to R ¹⁵ is a fluorine atom; R ²¹ to R ²⁷ are each a hydrogen atom or a fluorine atom, and at least one of R ²¹ to R ²⁷ is a fluorine atom.

Representative examples of the first additive are as follows:

[Chemical Formula 1-1-1]

.

.

Second additive

In the above chemical formula 2, R ³ and R ⁴ are each independently a halogen atom or a fluoroalkyl group having 1 to 10 carbon atoms.

For example, both R ³ and R ⁴ can be fluorine atoms.

Representative examples of the second additive are as follows:

[Chemical Formula 2-1]

The second additive represented by the chemical formula 2-1 above is lithium difluoro(oxalato)borate (LiDFOB).

Third additive

In the above chemical formula 3, R ⁵ and R ⁶ are each independently a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

For example, R ⁵ can be a fluoroalkyl group or a perfluoroalkyl group having 2 carbon atoms.

Additionally, R ⁶ can be a fluoroalkyl group or a perfluoroalkyl group having 3 carbon atoms.

The above third additive can be represented by the following chemical formula 3-1:

[Chemical Formula 3-1]

In the chemical formula 3-1, R ⁵¹ to R ⁵⁵ are each a hydrogen atom or a fluorine atom, and at least one of R ³¹ to R ³⁵ is a fluorine atom; R ⁶¹ to R ⁶⁷ are each a hydrogen atom or a fluorine atom, and at least one of R ⁴¹ to R ⁴⁷ is a fluorine atom.

Representative examples of the third additive are as follows:

[Chemical Formula 3-1-1]

.

.

Contents of the first to third additives

The first additive may be included in an amount of 1 to 20 wt%, 1 to 15 wt%, or 1 to 10 wt% based on the total amount of the electrolyte.

If the first additive is included in an excessive amount exceeding the above range, the viscosity of the electrolyte containing the first additive may excessively increase, so that the wettability for the positive and negative electrodes may actually decrease. On the other hand, if the content of the first additive is included in a small amount below the above range, the effect as a surfactant may be minimal.

The second additive may be included in an amount of 0.1 to 10 wt%, 0.5 to 5 wt%, or 1 to 2 wt% based on the total amount of the electrolyte.

If the second additive is included in an excessive amount exceeding the above range, a side reaction may occur. On the other hand, if the content of the second additive is included in a small amount below the above range, the effect may be minimal.

The third additive may be included in an amount of 1 to 10 wt%, 1 to 7 wt%, or 1 to 5 wt% based on the total amount of the electrolyte.

If the third additive is included in an excessive amount exceeding the above range, the viscosity of the electrolyte containing the third additive may increase excessively, and the wettability for the positive and negative electrodes may rather decrease. On the other hand, if the content of the third additive is included in a small amount below the above range, the effect as a surfactant may be minimal.

With respect to 10 parts by weight of the first additive, the second additive may be included in an amount of 1 to 100 parts by weight, and the third additive may be included in an amount of 1 to 100 parts by weight.

For example, with respect to 10 parts by weight of the first additive, the second additive may be included in an amount of 2 to 50 parts by weight, and the third additive may be included in an amount of 2 to 50 parts by weight.

For example, with respect to 10 parts by weight of the first additive, the second additive may be included in an amount of 5 to 20 parts by weight, and the third additive may be included in an amount of 5 to 20 parts by weight.

In this range, the effects of the first additive to the third additive can be harmonized.

Non-aqueous organic solvent

The above non-aqueous organic solvent acts as a medium through which ions involved in the electrochemical reaction of the battery can move.

The above non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, or alcohol-based solvent, an aprotic solvent, or a combination thereof.

Examples of the carbonate solvent that can be used include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), etc. Examples of the ester solvent that can be used include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, propyl propionate, decanolide, mevalonolactone, valerolactone, caprolactone, etc. Examples of ether solvents that can be used include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, etc. In addition, cyclohexanone can be used as a ketone solvent. Examples of alcohol solvents that can be used include ethyl alcohol, isopropyl alcohol, etc., and examples of aprotic solvents that can be used include nitriles such as R-CN (where R is a linear, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms and may include a double bond, an aromatic ring, or an ether group); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane and 1,4-dioxolane; and sulfolanes.

The above non-aqueous organic solvents can be used alone or in combination of two or more.

In the latter case, the non-aqueous organic solvent may include a carbonate-based solvent and a propionate-based solvent.

The entire propionate solvent may be included in an amount of 70% by volume or more based on the total amount of the non-aqueous organic solvent. In this case, the high voltage and/or high temperature characteristics of the lithium secondary battery may be improved.

For example, the non-aqueous organic solvent may be a mixed solvent of ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP).

Lithium salt

The above lithium salt is a substance that is dissolved in an organic solvent and acts as a source of lithium ions within the battery, enabling the basic operation of a lithium secondary battery and promoting the movement of lithium ions between the positive and negative electrodes.

LiPF ₆ can be used as the above lithium salt.

The concentration of the above lithium salt can be 0.1 M to 2.0 M.

Bipolar active material

As a cathode active material, a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound) can be used. Specifically, at least one of a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof can be used.

The above composite oxide may be a lithium transition metal composite oxide, and specific examples thereof include lithium nickel-based oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based compound, cobalt-free nickel-manganese-based oxide, or a combination thereof.

As an example, a compound represented by any one of the following chemical formulas can be used. Li _a A _1-b X _{b O 2-c} D _c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li _a Mn _2-b X b O 4 _-c D _c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li _a Ni _1-bc Co _b X _c O _2-α D _α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li _a Ni _1-bc Mn _b X _c O _2-α D _α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li _a Ni _b Co _c L ¹ _d G _e O ₂ (0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li _a NiG _b O ₂ (0.90≤a≤1.8, 0.001≤b≤0.1); Li _a CoG _b O ₂ (0.90≤a≤1.8, 0.001≤b≤0.1); Li _a Mn _1-b G _b O ₂ (0.90≤a≤1.8, 0.001≤b≤0.1); Li _a Mn ₂ G _b O ₄ (0.90≤a≤1.8, 0.001≤b≤0.1); Li _a Mn _1-g G _g PO ₄ (0.90≤a≤1.8, 0≤g≤0.5); Li _(3-f) Fe ₂ (PO ₄ ) ₃ (0≤f≤2); Li _a FePO ₄ (0.90≤a≤1.8).

In the chemical formula above, A is Ni, Co, Mn, or a combination thereof; X is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; and L ¹ is Mn, Al, or a combination thereof.

For example, the cathode active material may be a high-nickel cathode active material in which the nickel content is 80 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 94 mol% or more and 99 mol% or less, based on 100 mol% of metal excluding lithium in the lithium transition metal composite oxide. The high-nickel cathode active material can implement high capacity and thus can be applied to high-capacity, high-density lithium secondary batteries.

The cathode active material may include, for example, a lithium nickel-based oxide represented by the following chemical formula 11, a lithium cobalt-based oxide represented by the following chemical formula 12, a lithium iron phosphate-based compound represented by the following chemical formula 13, a cobalt-free lithium nickel-manganese-based oxide represented by the following chemical formula 14, or a combination thereof.

[Chemical Formula 11]

Li _a1 Ni _x1 M ¹ _y1 M ² _z1 O _{2- b1}

In the chemical formula 11, 0.9≤a1≤1.8, 0.3≤x1≤1, 0≤y1≤0.7, 0≤z1≤0.7, 0.9≤x1+y1+z1≤1.1, and 0≤b1≤0.1, and M ¹ and M ² are each independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

In the above chemical formula 1, 0.6≤x1≤1, 0≤y1≤0.4, and 0≤z1≤0.4, or 0.8≤x1≤1, 0≤y1≤0.2, and 0≤z1≤0.2.

[Chemical Formula 12]

Li _a2 Co _x2 M ³ _y2 O _{2- b2}

In the chemical formula 12, 0.9≤a2≤1.8, 0.7≤x2≤1, 0≤y2≤0.3, 0.9≤x2+y2≤1.1, and 0≤b2≤0.1, M ³ is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn, and Zr, and X is at least one element selected from the group consisting of F, P, and S.

[Chemical Formula 13]

Li _a3 Fe _x3 M ⁴ _y3 PO _{4- b3}

In the chemical formula 13, 0.9≤a3≤1.8, 0.6≤x3≤1, 0≤y3≤0.4, and 0≤b3≤0.1, M ⁴ is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn, and Zr, and X is at least one element selected from the group consisting of F, P, and S.

[Chemical Formula 14]

Li _a4 Ni _x4 Mn _y4 M ⁵ _z4 O _{2- b4}

In the chemical formula 14, 0.9≤a2≤1.8, 0.8≤x4<1, 0<y4≤0.2, 0≤z4≤0.2, 0.9≤x4+y4+z4≤1.1, and 0≤b4≤0.1, and M ⁵ is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is at least one element selected from the group consisting of F, P, and S.

In particular, the electrolyte of the above-described embodiment can excellently improve the high-voltage and/or high-temperature characteristics of a battery using a lithium cobalt-based oxide represented by the chemical formula 12.

anode

A cathode for a lithium secondary battery may include a current collector and a cathode active material layer formed on the current collector. The cathode active material layer includes a cathode active material and may further include a binder and/or a conductive material.

For example, the above anode may further include an additive that can act as a sacrificial anode.

The content of the positive electrode active material may be 90 wt% to 99.5 wt% with respect to 100 wt% of the positive electrode active material layer, and the contents of the binder and conductive material may be 0.5 wt% to 5 wt%, respectively, with respect to 100 wt% of the positive electrode active material layer.

The above binder serves to adhere the positive electrode active material particles well to each other and also to adhere the positive electrode active material well to the current collector. Representative examples of the binder include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, epoxy resin, (meth)acrylic resin, polyester resin, nylon, etc.

The conductive material is used to provide conductivity to the electrode, and any material that does not cause a chemical change and is electronically conductive in the battery may be used. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanofibers, and carbon nanotubes; metal-based materials containing copper, nickel, aluminum, and silver in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

Al may be used as the above current collector, but is not limited thereto.

Negative active material

The negative active material includes a material capable of reversibly intercalating/deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.

The material capable of reversibly intercalating/deintercalating the lithium ions may include a carbon-based negative electrode active material, for example, crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake-like, spherical, or fibrous form, and examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, and the like.

As the above lithium metal alloy, an alloy of lithium and a metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn can be used.

As the material capable of doping and dedoping the lithium, a Si-based negative electrode active material or a Sn-based negative electrode active material can be used. The Si-based negative electrode active material can be silicon, a silicon-carbon composite, SiOx (0 < x < 2), a Si-Q alloy (wherein Q is selected from an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element (excluding Si), a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and combinations thereof), or a combination thereof. The Sn-based negative electrode active material can be Sn, SnO ₂ , a Sn-based alloy, or a combination thereof.

The silicon-carbon composite may be a composite of silicon and amorphous carbon. According to one embodiment, the silicon-carbon composite may be in the form of silicon particles and amorphous carbon coated on the surface of the silicon particles. For example, it may include secondary particles (cores) in which silicon primary particles are assembled, and an amorphous carbon coating layer (shell) positioned on the surface of the secondary particles. The amorphous carbon may also be positioned between the silicon primary particles, so that, for example, the silicon primary particles may be coated with amorphous carbon. The secondary particles may be dispersed and present in an amorphous carbon matrix.

The silicon-carbon composite may further include crystalline carbon. For example, the silicon-carbon composite may include a core including crystalline carbon and silicon particles and an amorphous carbon coating layer positioned on the surface of the core.

The above Si-based negative electrode active material or Sn-based negative electrode active material can be used in a mixture with a carbon-based negative electrode active material.

cathode

A negative electrode for a lithium secondary battery includes a current collector and a negative electrode active material layer positioned on the current collector. The negative electrode active material layer includes a negative electrode active material and may further include a binder and/or a conductive material.

For example, the negative active material layer may include 90 to 99 wt% of the negative active material, 0.5 to 5 wt% of the binder, and 0 to 5 wt% of the conductive material.

The above binder serves to adhere the negative active material particles well to each other and also to adhere the negative active material well to the current collector. The binder may be a non-aqueous binder, an aqueous binder, a dry binder, or a combination thereof.

The above non-aqueous binder may include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene propylene copolymer, polystyrene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide or combinations thereof.

The above-mentioned aqueous binder may be selected from styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluoroelastomer, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, ethylene propylene diene copolymer, polyvinyl pyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

When using an aqueous binder as the above-mentioned negative binder, a cellulose-based compound capable of imparting viscosity may be further included. As the cellulose-based compound, one or more types of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or an alkali metal salt thereof may be mixed and used. As the above-mentioned alkali metal, Na, K or Li may be used.

The above dry binder is a polymeric material capable of being fiberized, and may be, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, or a combination thereof.

The above conductive material is used to provide conductivity to the electrode, and any material that does not cause a chemical change and is electronically conductive in the battery to be formed can be used. Specific examples include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanofibers, and carbon nanotubes; metal-based materials including copper, nickel, aluminum, and silver in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

The negative electrode current collector may be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.

Separator

Depending on the type of lithium secondary battery, a separator may exist between the positive and negative electrodes. Such separators may include polyethylene, polypropylene, polyvinylidene fluoride, or multilayer films of two or more layers thereof, and of course, mixed multilayer films such as a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, or a polypropylene/polyethylene/polypropylene three-layer separator may be used.

The above separator may include a porous substrate and a coating layer including an organic material, an inorganic material, or a combination thereof positioned on one or both sides of the porous substrate.

The above porous substrate may be a polymer film formed of any one polymer selected from polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyamide, polyimide, polycarbonate, polyether ketone, polyarylether ketone, polyetherimide, polyamideimide, polybenzimidazole, polyether sulfone, polyphenylene oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, glass fiber, Teflon, and polytetrafluoroethylene, or a copolymer or mixture of two or more thereof.

The above organic material may include a polyvinylidene fluoride-based antibody or a (meth)acrylic polymer.

The above inorganic substances are Al ₂ O ₃ , SiO ₂ , TiO ₂ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, GaO, ZnO, ZrO ₂ , Y ₂ O ₃ , It may include inorganic particles selected from, but not limited to, SrTiO ₃ , BaTiO ₃ , Mg(OH) ₂ , boehmite, and combinations thereof.

The above organic and inorganic substances may be mixed and present in one coating layer, or may be present in a laminated form with a coating layer containing an organic substance and a coating layer containing an inorganic substance.

Lithium secondary battery

Lithium secondary batteries can be classified into cylindrical, square, pouch, coin, etc. shapes depending on their form. FIGS. 1 to 4 are schematic diagrams illustrating lithium secondary batteries according to one embodiment, wherein FIG. 1 can be said to be a cylindrical battery, FIG. 2 a square battery, and FIGS. 3 and 4 a pouch battery. Referring to FIGS. 1 to 4, a lithium secondary battery (100) may include an electrode assembly (40) having a separator (30) interposed between a positive electrode (10) and an negative electrode (20), and a case (50) in which the electrode assembly (40) is built. The positive electrode (10), the negative electrode (20), and the separator (30) may be impregnated with an electrolyte (not shown). The lithium secondary battery (100) may include a sealing member (60) that seals the case (50) as shown in FIG. 1. In addition, in FIG. 2, the lithium secondary battery (100) may include a positive lead tab (11), a positive terminal (12), a negative lead tab (21), and a negative terminal (22). As in FIGS. 3 and 4, the lithium secondary battery (100) may include electrode tabs (70), i.e., a positive tab (71) and a negative tab (72), which serve as electrical paths for inducing current formed in the electrode assembly (40) to the outside.

A lithium secondary battery according to one embodiment of the present invention may be applied to automobiles, mobile phones, and/or various types of electrical devices, but the present invention is not limited thereto.

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only examples of the present invention, and the present invention is not limited to the following examples.

Examples and Comparative Examples

An electrolyte and a lithium secondary battery were manufactured using the following method.

Example 1

(1) Preparation of electrolyte

An electrolyte was prepared by dissolving 1.3 M LiPF ₆ in a non-aqueous organic solvent containing ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP) in a volume ratio of 10:15:30:45, and adding 5 wt% of a first additive, 1 wt% of a second additive, and 1 wt% of a third additive.

As the first additive, a compound represented by the following chemical formula 1-1-1 was used, as the second additive, a compound represented by the following chemical formula 2-1 was used, and as the third additive, a compound represented by the following chemical formula 3-1-1 was used:

[Chemical Formula 1-1-1]

.

.

1,1,2,2-Tetrafluoroethyl2,2,3,3-tetrafluoropropylether (CAS No.: 16627-68-2)

[Chemical Formula 2-1]

Lithium difluoro(oxalato)borate(LiDFOB, CAS No.: 409071-16-5)

[Chemical Formula 3-1-1]

Perfluoro(2-methyl-3-pentanone) (CAS No.: 756-13-8)

(2) Manufacturing of lithium secondary batteries

LiCoO ₂ as a cathode active material, polyvinylidene fluoride as a binder, and acetylene black as a conductive material were mixed in a weight ratio of 96:3:1, respectively, and dispersed in N -methyl pyrrolidone to prepare a cathode active material slurry.

The above positive electrode active material slurry was coated on a 15 ㎛ thick Al foil, dried at 100°C, and then pressed to manufacture a positive electrode.

Artificial graphite was used as a negative active material, and the negative active material, styrene-butadiene rubber binder, and carboxymethyl cellulose were mixed in a weight ratio of 98:1:1, respectively, and dispersed in distilled water to prepare a negative active material slurry.

The above negative active material slurry was coated on a 10 μm thick Cu foil, dried at 100°C, and pressed to manufacture a negative electrode. At this time, the composite density of the negative electrode was set to 1.7 g/cc.

An electrode assembly was manufactured by assembling the positive electrode and the negative electrode and a separator made of polyethylene material having a thickness of 10 μm, and the electrolyte was injected to manufacture a lithium secondary battery.

Example 2

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 10 wt% of the first additive, 1 wt% of the second additive, and 1 wt% of the third additive were added during the manufacture of the electrolyte.

Example 3

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 10 wt% of the first additive, 1 wt% of the second additive, and 2 wt% of the third additive were added during the manufacture of the electrolyte.

Example 4

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 10 wt% of the first additive, 1 wt% of the second additive, and 2 wt% of the third additive were added when manufacturing the electrolyte, and that the density of the composite was set to 1.75 g/cc when manufacturing the negative electrode.

Example 5

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 10 wt% of the first additive, 1 wt% of the second additive, and 2 wt% of the third additive were added when manufacturing the electrolyte, and that the density of the composite was set to 1.8 g/cc when manufacturing the negative electrode.

Comparative Example 1

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that no additives were added during the manufacture of the electrolyte and the composite density was set to 1.65 g/cc during the manufacture of the negative electrode.

Comparative Example 2

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that no additives were added during the manufacture of the electrolyte and the composite density was set to 1.67 g/cc during the manufacture of the negative electrode.

Comparative Example 3

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that no additives were added during the manufacture of the electrolyte and the composite density was set to 1.7 g/cc during the manufacture of the negative electrode.

Comparative Example 4

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the second and third additives were not added when manufacturing the electrolyte, 10 wt% of the first additive was added, and the density of the composite was set to 1.7 g/cc when manufacturing the negative electrode.

Comparative Example 5

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the first and third additives were not added when manufacturing the electrolyte, 1 wt% of the second additive was added, and the density of the composite was set to 1.7 g/cc when manufacturing the negative electrode.

Comparative Example 6

An electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the first and second additives were not added when manufacturing the electrolyte, 1 wt% of the third additive was added, and the density of the composite was set to 1.7 g/cc when manufacturing the negative electrode.

Evaluation example

The cathode and lithium secondary battery were evaluated in the following manner.

Evaluation 1: Impregnation of electrolyte into the cathode

A negative electrode according to Example 1 was manufactured into a specimen measuring 3 cm x 5 cm in length x width. 0.02 g of the electrolyte according to Example 1 was dropped onto the specimen and left for 1 minute. Thereafter, the amount of the electrolyte immersed in the specimen among 100 wt% of the electrolyte dropped onto the specimen was evaluated as a numerical value from 0 to 5 according to the following criteria, and the evaluation results are recorded in Table 1 below.

0: When the amount of electrolyte immersed in the specimen is 0 wt% or more and less than 10 wt%

1: When the amount of electrolyte immersed in the specimen is 10 wt% or more and less than 20 wt%

2: When the amount of electrolyte immersed in the specimen is 20 wt% or more and less than 40 wt%

3: When the amount of electrolyte immersed in the specimen is 40 wt% or more and less than 60 wt%

4: When the amount of electrolyte immersed in the specimen is 60 wt% or more and less than 80 wt%

5: When the amount of electrolyte immersed in the specimen is 80 wt% or more and less than 100 wt%

Examples 2 to 5 and Comparative Examples 1 to 6 were evaluated using the same method, and the evaluation results are shown in Table 1 below.

Density of the cathode composite (g/cc) Content of additives in electrolyte (weight%) For the cathode
Impregnation of electrolyte Additive 1 Second additive Third additive Comparative Example 1 1.65 0 0 0 3 Comparative Example 2 1.67 0 0 0 2 Comparative Example 3 1.7 0 0 0 1 Comparative Example 4 1.7 10 0 0 1 Comparative Example 5 1.7 0 1 0 1 Comparative Example 6 1.7 0 0 1 1 Example 1 1.7 5 1 1 3 Example 2 1.7 10 1 1 4 Example 3 1.7 10 1 2 5 Example 4 1.75 10 1 2 5 Example 5 1.8 10 1 2 4

Evaluation 2: Evaluation of high temperature and high voltage charge/discharge cycle characteristics

The lithium secondary battery was subjected to 200 charge/discharge cycles under the conditions of 45℃, 2.0C charge (CC/CV, 4.53 V, 0.025 C Cut-off) / 1.0C discharge (CC, 3 V Cut-off).

The thickness increase rate is calculated according to Equation 1 below, and the capacity retention rate is calculated according to Equation 2 below, and the results are shown in Table 2 below.

[Formula 1]

Thickness increase rate = {(Full thickness after 200 cycles) - (Full thickness after 1 cycle)}/(Full thickness after 1 cycle) * 100

In the above equation 1, the “full charge thickness” refers to the thickness of the lithium secondary battery measured after charging to 100% SOC (a state in which the battery is charged to 100% charge capacity when the total charge capacity of the battery is 100%) after each cycle.

[Formula 2]

Capacity retention rate = (discharge capacity after 200 cycles / discharge capacity after 1 cycle) * 100

Density of the cathode composite (g/cc) Content of additives in electrolyte (weight%) Lithium secondary battery
High temperature and high voltage charge/discharge characteristics Additive 1 Second additive Third additive Thickness Increase Rate (%) Capacity retention rate (%) Comparative Example 1 1.65 0 0 0 13.1 87 Comparative Example 2 1.67 0 0 0 15.9 81 Comparative Example 3 1.7 0 0 0 15.8 83 Comparative Example 4 1.7 10 0 0 16.0 81 Comparative Example 5 1.7 0 1 0 15.5 75 Comparative Example 6 1.7 0 0 1 17.8 72 Example 1 1.7 5 1 1 13.7 90 Example 2 1.7 10 1 1 10.5 89 Example 3 1.7 10 1 2 8.8 92 Example 4 1.75 10 1 2 9.3 91 Example 5 1.8 10 1 2 11.5 89

synthesis

Referring to Tables 1 and 2 above, when using an electrolyte without any additives (Comparative Examples 1 to 3), as the density of the negative electrode mixture increases from 1.65 g/cc to 1.7 g/cc, the impregnation property of the electrolyte into the negative electrode decreases, the thickness of the battery increases during high-temperature and high-voltage charge/discharge, and the capacity retention rate during high-temperature storage decreases.

However, when the composite density of the negative electrode is the same as 1.7 g/cc, and when an electrolyte containing the first to third additives is used simultaneously (Examples 1 to 3) compared to when an electrolyte without any additives is used (Comparative Example 3), the impregnation property of the electrolyte into the negative electrode increases, and the thickness of the battery decreases and the lifespan decreases during high-temperature and high-voltage charge/discharge.

Meanwhile, when using an electrolyte containing only one of the first to third additives (Comparative Examples 4 to 6), an SEI film is formed unstably on the surface of the negative electrode, causing lithium dendrites to grow, and thus the capacity retention rate during high-temperature and high-voltage charge/discharge is rapidly reduced. Therefore, it is necessary to use an electrolyte containing the first to third additives simultaneously.

Furthermore, when using an electrolyte containing the first to third additives simultaneously, even if the composite density of the negative electrode is increased from 1.7 g/cc to 1.8 g/cc (Examples 4 and 5), the increase in the thickness of the battery and the decrease in the lifespan are suppressed during high-temperature and high-voltage charge and discharge.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications may be made within the scope of the claims, the detailed description of the invention, and the attached drawings, which also fall within the scope of the present invention.

100: Lithium secondary battery 10: Cathode
11: Positive lead tab 12: Positive terminal
20: Negative 21: Negative lead tab
22: Negative terminal 30: Separator
40: Electrode assembly 50: Case
60: Sealing member 70: Electrode tab
71: Positive tab 72: Negative tab

Claims (17)

A cathode comprising a cathode active material;
A negative electrode comprising a negative active material; and
Including electrolyte,
The composite density of the above negative electrode is 1.7 g/cc or more,
The above electrolyte is
lithium salt;
non-aqueous organic solvent;
A first additive represented by the following chemical formula 1;
A second additive represented by the following chemical formula 2; and
Containing a third additive represented by the following chemical formula 3,
Lithium secondary battery:
[Chemical Formula 1]

In the above chemical formula 1,
R ¹ and R ² are each independently a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms;
[Chemical formula 2]

In the above chemical formula 2,
R ³ and R ⁴ are each independently a halogen atom or a fluoroalkyl group having 1 to 10 carbon atoms;
[Chemical Formula 3]

In the above chemical formula 3,
R ⁵ and R ⁶ are each independently a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.
In paragraph 1,
The above first additive is a lithium secondary battery represented by the following chemical formula 1-1:
[Chemical Formula 1-1]

In the above chemical formula 1-1,
R ¹¹ to R ¹⁵ are each a hydrogen atom or a fluorine atom, wherein at least one of R ¹¹ to R ¹⁵ is a fluorine atom;
R ²¹ to R ²⁷ are each a hydrogen atom or a fluorine atom, and at least one of R ²¹ to R ²⁷ is a fluorine atom.
In paragraph 1,
The above first additive is a lithium secondary battery represented by the following chemical formula 1-1-1:
[Chemical Formula 1-1-1]

.
In paragraph 1,
Lithium secondary battery where R ³ and R ⁴ are both fluorine atoms.
In paragraph 1,
The third additive is a lithium secondary battery represented by the following chemical formula 3-1:
[Chemical Formula 3-1]

In the above chemical formula 3-1,
R ⁵¹ to R ⁵⁵ are each a hydrogen atom or a fluorine atom, and at least one of R ³¹ to R ³⁵ is a fluorine atom;
R ⁶¹ to R ⁶⁷ are each a hydrogen atom or a fluorine atom, and at least one of R ⁴¹ to R ⁴⁷ is a fluorine atom.
In paragraph 1,
The third additive is a lithium secondary battery represented by the following chemical formula 3-1-1:
[Chemical Formula 3-1-1]

.
In paragraph 1,
A lithium secondary battery, wherein the first additive is included in an amount of 1 to 20 wt% based on the total amount of the electrolyte.
In paragraph 1,
A lithium secondary battery, wherein the second additive is included in an amount of 1 to 10 wt% based on the total amount of the electrolyte.
In paragraph 1,
A lithium secondary battery, wherein the third additive is included in an amount of 1 to 10 wt% based on the total amount of the electrolyte.
In paragraph 1,
A lithium secondary battery, wherein the second additive is contained in an amount of 1 to 100 parts by weight, and the third additive is contained in an amount of 1 to 100 parts by weight, relative to 10 parts by weight of the first additive.
In paragraph 1,
A lithium secondary battery wherein the non-aqueous organic solvent includes a carbonate solvent and a propionate solvent.
In Article 11,
A lithium secondary battery, wherein the propionate solvent is contained in an amount of 70% by volume or more based on the total amount of the non-aqueous organic solvent.
In paragraph 1,
The above lithium salt is LiPF ₆ , a lithium secondary battery.
In paragraph 1,
A lithium secondary battery wherein the concentration of the lithium salt is 0.1 M to 2.0 M.
In paragraph 1,
A lithium secondary battery wherein the positive electrode active material comprises lithium nickel-based oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based compound, cobalt-free nickel-manganese oxide, or a combination thereof.
In paragraph 1,
A lithium secondary battery wherein the negative electrode active material includes a carbon-based negative electrode active material, a Si-based negative electrode active material, or a combination thereof.
In paragraph 1,
A lithium secondary battery having an upper limit charge voltage of 4.5 V or higher.